Basic monoazo and disazo dyestuffs containing a hydrazinium group



United States Patent 3,341,514 BASIC MONOAZO AND DISAZO DYESTUFFS CONTAINING A HYDRAZINIUM GROUP Roland Entschel and Curt Mueller, Basel, and Walter Wehrli, Riehen, Switzerland, assignors to Sandoz Ltd. (also known as Sandoz A.G.), Basel, Switzerland No Drawing. Filed Apr. 29, 1966, Ser. No. 546,192 Claims priority, application Switzerland, Apr. 21, 1961, 4,709/61; Jan. 12, 1962, 359/62; May 3, 1963, 5,588/ 63; Jan. 16, 1964, 479/64; Feb. 7, 1964, 1,482/64 6 Claims. (Cl. 260-465) The present invention is a continuation-in-part application to our co-pending applications Ser. No. 188,837, filed on April 19, 1962, and now US. Patent 3,252,967; Ser. No. 188, 889, filed on April 19, 1962, and now U.S. Patent 3,252,965; Ser. No. 250,787, filed on Jan. 11, 1963, now abandoned; Ser. No. 250,788, filed on Jan. 11, 1963, now abandoned; Ser. No. 250,789, filed on Jan. 11, 1963, now abandoned; our continuation-in-part application Ser. No. 300,068, filed on Aug. 5, 1963, now abandoned; our continuation-in-part application, Ser. No. 306,306, filed on Sept. 3, 1963; our continuation-in-part application Ser. No. 306,321, filed on Sept 3, 1963, and now abandoned; our continuation-in-part application Ser. No. 344,557, filed on Feb. 13, 1964, and now abandoned, and relates to basic dyestuffs and process for their production.

This invention relates to basic dyes of the formula wherein A is a member selected from the group consisting of a radical of a monoazo and a disazo dyestuif, said dyestuffs being free from carboxylic acid and sulfonic acid groups,

y is a bridge member selected from the group consisting group consisting of hy- These new dyes of Formula I can conveniently be pre-. pared by replacing, or converting, it substituents Z'in a compound of the formula -fy )n by, or into, 11 groups of the formula Re I a /I|\IN H (III) R2 wherein B represents A or the radical of a compound capable of the formation of a monoazo or a disazo dye A, and Z a substituent which can be replaced by, or converted into, a group of Formula III upon which the reaction product is converted into a monoor diazo dye in cases where B represents the radical of a compound capable of the formation of a dye. A preferred mode of operation of the present process for the production of new basic anonoor disazo dyes comprises reacting 1 mol of a compound of the formula wherein E represents the acid radical of an ester, with n mols of a compound of the formula and converting the reaction product into a monoor disazo dye when B represents a radical capable of the formation of a dye.

Another mode of operation of the process comprises reacting 1 mol of a compound of the formula -t;v- )n with n mols of a compound of the formula R -NH-HN-R (VI) by reacting 1 mol of an amine of the formula B--y-N\ R2 n withn mols of a halogen amine, and, when B represents a radical capable of dye formation, converting the reaction product into a monoor disazo dye; or by reacting 1 mol of a compound of the formula R E y-N with n mols of a halogen amine, quaternizing the reaction product and, when B represents a radical capable of dye formation, converting the product into a monoor disazo dye; or by reacting 1 mol of a compound of the formula with n mols of a halogen amine, quaternizing the reaction product with an agent not yielding methyl groups, and converting the product into a monoor disazo dye when B stands for a radical capable of dye formation. In the two lattermodes of operation quaternation and conversion into a dye can be carried out in either order.

Monoazoor disazo dye radicals containing metal atoms bound by coordination links can also be used. The ortho, ortho'- dihydroxy or ortho, ortho-hydroxyamino compounds, together with the ions of heavy metals such as Fe, Cu, Ni, Cr, Co, Mn are suitable for the formation of 1:1 and 1:2 metal-complex dyes.

The components B which are suitable for the formation of the monoazo or disazo dye radical A are preferably those which can be converted into the above-mentioned azo dye radicals by reaction with a diazonium salt or a coupling compound.

The azo coupling reaction is carried out in the known way, preferably in a weakly alkaline to acid medium which may be buffered if necessary.

Other suitable components B are compounds which contain a functional group or a group convertible into a functional group. These compounds are reacted with the components used for the formation of the monazo or disazo dye radical A to give the final dye of Formula I, e.g. by a condensation reaction.

Al'kylating agents which are suitable for converting the reaction products of the compounds of Formulae Xor XI and halogen amine, or of a compound of Formula IV and a compound of Formula VI into the dye salts obtainable by the present .process are e.g., the esters of strong mineral acids and organic sulfonic acids, alkyl chlorides, alkyl bromides and alkyl iodides, aralkyl halides, rat-halogenated esters of low molecular fatty acid, dialkyl sulfates, alkyl esters of low molecular alkanesul-fo'nic acids, e.g. methane-, ethaneor butane-sulfonic acids, the esters of benzenesulfonie acids which may be further substituted, such as methyl, ethyl, propyl and n-butyl esters of benzenesulfonic, 2- or 4-methylbenzenesulfonic acid, 4-chlorobenzenesulfo'nic acid or 3- or 4-nitro benzenesulfonic acid, methylor ethylchloride, methylor ethyl'bromide and methylor ethyliodide or dimethylor diethylsulfate, methylor ethylesters of low molecular alkansulfonic acid or of benzene sulfonic acids.

Alkylation or quaternation is carried out preferably in an inert solvent, or in aqueous suspension, or without solvent in an excess of the alkylating agent and at increased temperatures with the addition of a bufiering agent if necessary.

The anion Or anions X may be organic or inorganic ions, e.g. the ions of methyl-sulfate, sulfate, disulfate, perchlorate, chloride, bromide, iodide, phosphorus-molybdate, phosphorus-tungsten-molybdate, benzene-sulfonate, oxalate, maleinate, acetate, propionate, methansulfonate, chloroacetate, or 4-chlorobenzene-sulfonate.

R and R together with the adjacent N can form a heterocyclic ring system without y,e.g. a pyrrolidine, a piperidine, piperazine, a morpholine, a 1,2,4-triazol or an ethylene imine grouping etc.

Examples of suitable acid radicals E are those of sulfuric acid (E=SO H),a sulfonic acid (E=SO R where R is substitutedor unsubstituted hydrocarbon radical), and hydrogen sulfide (E=SH), but preferably the radicals of the halogen hydracids (E=Cl, Br etc.) are employed.

The reaction of a compound of Formula IV with a hydrazine of the Formula V or VI is efiected preferably in an organic solvent and at temperatures of 50 C. to +250 C. The reaction can also be carried out in aqueous medium, if necessary with the addition of an organic solvent, or without solvent at the above-stated temperatures.

The reaction of an amine of Formulae X, X1 or XII with a halogenamine is carried out preferably in an organic solvent and at temperatures of 50 C. to +80 C. The reaction can also be effected in aqueous medium, if necessary with the addition of an organic solvent, at the above-stated temperatures.

The halogenamine can be employed either in gaseous form or in solution in an organic solvent, in water, or in a solvent-Water mixture.

The dyes formed are separated by one of the basic operations such as filtration, evaporation and filtration, precipitation from a suitable medium and filtration.

The new dyes are excellent for dyeing, padding and printing materials of polymers containing more than 80% acrylonitrile, e.g. polyacrylonitrile, e.g. Orlon (registered trademark), and copolymers containing 8095% acrylonitrile and 20-25% vinyl acetate, methyl acrylate or methyl methacrylate. These products are marketed under the following names, most of which are registered trademarks: Acrilan (the copolymer of acylonitrile and 15% vinyl acetate or vinyl pyridine), Orlon, Dralon, Courtelle, Crylor, Oynel, etc. a

The dyeings on these materials obtained with the dyes of the process possess good fastness to light, washing, perspiration, sublimation, pleating, decatizing, pressing, water, sea water, bleaching, dry cleaning, cross dyeing and solvents. Some of the dyes are very good soluble in water.

The dyes of the ,present process are dyed to best advantage from aqueous medium, and it is preferable for the medium to be neutral or acid and of boiling temperature.

The commercially available retarding agents can be used in dyeing without adverse effect, though the new dyes produce perfectly level dyeings on the above-named polymers and copolymers without the addition of these agents. The dyes can be applied in closed equipment and under pressure, as they are highly stabile in water to prolonged boiling. They also give very good dyeings on blend fabrics containing a polyacrylonitrile fiber or acrylonitrile copolymer fiber as one of the components. A selected number of the new dyes are suitable for dyeing polyacrylonitrile in the mass in shades fast to light and wet fastness treatments. The dyes of the present process which possess good solubility in organic solvents are suitable for the coloration of oils, paint and lacquer media, and plastics, and for the dyeing of fiber-forming materials in the spinning solution. They have many other uses, for example, the dyeing of tannin-treated cotton, wool, silk, regenerated cellulose, synthetic polyamide fibers, and paper; at all stages of manufactures it has been found that mixtures of two or more dyes of Formula I can be used with good success. The new dyes are well suited for combination, so that dye salts of the same or different dye classes can be used for producing widely different shades.

The azo dyes obtained by the present process may belong, for example, to the benzene-azo-benzene, benzeneazo-naphthalene, benzene azo pyrazolone, benzene-azoacylacetic acid arylamide, benzene-azo-phenyl, benzeneazo-diphenyl, benzene-azo-benzene-azo-phenol, thiazoleazo-benzene, thia diazol azo pyrazolone, pyridine-azoindole, benzene-azo-tetrahydroquinoline, benz thiazol-azotetrahydroquinoline, thiazol-azo-tetrahydroquinoline, benzene-azo-indole, benzene-azo-quinoline, benzene-azo-pyrazolidinedione, benzene azo indanedione, benzene-azopyrrole, benzene-azo-benzo-tetrahydroquinoline, or quinoline-azo-benzene series etc. They can be produced by the known methods, either by coupling diazotized amines with azo components, or by oxidation coupling. The hydrazinium group can be linked to the diazoand/or the azo component, in certain cases alongside other cationic groups, e.g. ammonium or cycloammonium groups.

Diazo compounds of the benzene, naphthalene and heterocyclic series are suitable for the production of the azo dyes of the present process. The substituents in these compounds are preferably those which are employed in the known disperse (acetate) and polyester dyes. Particularly suitable are chlorine, bromine, fluorine, nitrile, nitro, alkyl, trihalogenalkyl, alkylsulfonyl, sulfonamide, monoalkyl and dialkyl-sulfonamide, carbalkoxy, carboxylic acid amide, hydroxyl, alkoxy and carbalkoxy groups.

Suitable coupling components are the derivatives of the benzene, naphthalene and heterocyclic series and components having an active methylene group. Particularly suitable are the substituted aminobenzene derivatives which may be further substituted by alkyl groups and the derivatives substituted in the aromatic nucleus by e.g. substituted or unsubstituted alkyl, alkoxy, halogen, cyan, trifluoromethyl, alkanoylamino, alkylsulfonylamino etc. The term alkyl radical refers not only to radicals such as methyl, ethyl, propyl and butyl, but also to their substitution products (cf. E. de Barry, Anthracene and EXAMPLE 1 32.2; parts of the chloride of 1-amino-2-chloro-4-N- methyl-N-[a-N,N-diethylhydrazinio acetyH-aminobenzene are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at with 100 parts of normal sodium nitrite solution. The clear diazo solution is added dropwise in 30 minutes to an ice-cold solution consisting of 13.2 parts of l-hydroxy-4-methylbenzene, 200 parts, of water, 40 parts of 25% aqueous ammonia solution and parts of a mixture of pyridine bases. Stirring is continued at 0 until the coupling reaction is completed. The new yellow dyestutf formed is precipitated from the reaction mass by neutralization with 10% hydrochloric acid and sodium chloride, and is then filtered 01f, dried and ground. If necessary the dyestutf can be purified by recrystallization, e.g. from ethyl alcohol. It is a yellow brown powder which dissolves in water with a yellow coloration and is suitable for dyeing polyacrylonitrile fibers in yellow shades of very good light and wet fastness.

EXAMPLE 2 The 32.2 parts of the chloride of 1-amino-2-chloro-4- N methyl N-[a-N,N-diethylhydrazinio-acetyl] -aminobenzene of the preceding example are replaced by 38 parts of the chloride of 1-amino-2-bromo-4-N-ethyl-N[oz-N- amino pyrrolidinio acetyl]-amino-benzene and the procedure described in that example is carried out to yield a similar dyestuff which also dyes polyacrylonitrile fibers in yellow shades of very good light and wet fastness.

EXAMPLE 3 37.9 parts of the chloride of 1-amino-2-chloro-4-N- methyl-N-[a-N-aminomorpholinio acetyl]-amino benzene are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at 0 With 100 parts of normal sodium nitrite solution. The clear diazo solution is added dropwise in 30 minutes to an ice-cold solution of parts of 1-hydroxy-4-cyclohexyl-benzene, 200 parts of water, 40 parts of aqueous ammonia solution and 10 parts of a mixture of pyridine ba'ses. Stirring is continued at 0 until the coupling reaction is completed. The new yellow dyestulf formed is precipitated from the reaction mass by neutralization with 10% hydrochloric acid and sodium chloride, and is then filtered off, dried and ground. If necessary the dyestuff can be purified by recrystallization, eg from ethyl boiled for several hours with reflux condensation. On cooling the precipitated basic dyestuff is filtered off, dried and if necessary recrystallized. The new dyestuif dis solves in water with a yellow coloration and can be used for dyeing polyacrylonitrile fibers and containing polyacrylonitrile fibers in mixtures in yellow shades of very good light and wet fastness.

EXAMPLE 5 The 23.5 parts of 4-methyl -amino benzene azo-paracresol used in Example 4 are replaced by 27.8 parts of 4 methyl amino benzene-azo-para-tertiary butylphenol and the 6 parts of N,N-diethylhydrazine by 6 parts of N- aminopiperidine and the procedure of that example is followed. A similar dyestutf is obtained. which dyes polyacrylonitrile fibers in fast yellow shades.

EXAMPLE 6 30.3 parts of the chloride of 4-amino-benzene sulfonic acid N methyl N [it[N',N'-diethylhydrazinio]-ethylamide are dissolved in a mixture of 1170 parts of water and 35 parts of hydrochloric acid and diazotized at 0 with 100 parts of normal sodium nitrite solution. The clear diazo solution is run in 15 minutes with good stirring into an ice-cold solution of 45 parts of crystallized sodium acetate in 250 parts of water, in which 21.9 parts of 1-(3'-chlorophenyl)-3-methyl 5 pyrazolone is suspended in an extremely fine state. Stirring is continued at 0 and in the course of 2 hours the pH'value of the dyealcohol. It is' a yellow-brown powder which dissolves in water with a yellow coloration and is suitable for dyeing polyacrylonitrile fibers in yellow shades of very good light and wet fastness.

EXAMPLE 4 stulf suspension is increased to 6.0 by the addition of a sufficient amount of sodium carbonate. On completion of coupling the reaction mass is heated to 35 and the whole of the precipitated dyestuli is collected on a filter. On drying and grinding there is obtained a yellow powder which dissolves in water to give yellow solutions and is suitable for dyeing polyacrylonitrile fibers in very fast yellow shades.

EXAMPLE 7 The 21.9 parts of 1-(3-chlorophenyl) 3 methyl-5- pyrazolone used in the preceding Example 6 are replaced by 18.3 parts of 1-phenyl-3-methyl-5-pyrazolone and the procedure described in that example is'performed. The product is a similar dyestufl? which is also suitable for dyeing polyacrylonitrile fibers in very fast yellow shades.

EXAMPLE 8 30.3 parts of the chloride of 4-amino-benzene sulfonic acid N-methyl N ,8[N'N'-diethylhydrazinio] -ethylamide are dissolved in a mixture of 170 parts of water and 35 parts of 30% hydrochloric acid and diazotized at 0 with parts of normal sodium nitrite solution. The diazo solution, which contains no excess nitrous acid, is neutralized by dropwise addition of5% aqueous ammonia solution to the :pH value of 7.5. At the same temperature a solution of 30 parts of 2,S-dimethoxy-4-chloroacet0acetic anilide in 200 parts of ethyl alcohol is dropped in at an even rate in the course of 30 minutes with good stirring. Stirring is continued at 0 until the coupling reaction is completed, after which the dyestuif is isolated in the usual way. The basic dyestuff is dried and ground to a yellow coloration and is suitable for dyeing polyacrylonitrile fibers in very fast bright shades.

EXAMPLE 9 The 30.3 parts of the chloride of 4-amino-benzenesulfonic and N methyl N ,8[N';N' diethylhydrazinio]- ethylamide employed in Example 6 are replaced by 31.3 parts of the chloride of 4-amino-benzoic acid N-methyl- N-B[N,N'-dicyanoethylhydrazinio]ethylamide and the 21.9 parts of 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone by 11 parts of 3-methyl-5 pyrazolone, and the procedure of that example is followed in all other particulars. The dyestuif obtained is similar and dyes polyacrilonitrile fibers in fast yellow shades.

7 EXAMPLE 1o 24.2 parts of 4-nitrobenzoic anilide are dissolved in 60 parts of 94% sulfuric acid at a temperature lower than 10. When the solution clarifies, 14 parts of N-methylolchloroacetamide are added at below and in the course of the next 24 hours the reaction temperature is allowed to rise gradually to room temperature. The reaction mass is poured onto crushed ice, and the well crystallizing 4-nitrobenzoic acid 4 (chloroacetaminomethyD- anilide of the formula is filtered off and dried in vacuum.

44 parts of Compound B are reduced to the corresponding amino compound and this diazotized in aqueous hydrochloric acid solution at 0 by means of sodium nitrite. The diazo solution is freed from excess nitrous acid and at 0 a sufiicient amount of sodium acetate solution is added to obtain the pH value of 3.0. At the same temperature a solution of 13.2 parts of Z-methyl-indol in 60 parts of glacial acetic acid is added dropwise in 20 minutes and the reaction mass is stirred at 0 until completion of the reaction. The yellow basic dyestuff formed is isolated. It dyes polyacrylonitrile fibers in very fast shades.

Dyeing Example A 20 parts of the dye obtained according to Example 1 are intimately mixed with 80 parts of dextrin in a ball mill for 48 hours. 1 part of this preparation is pasted with 1 part of acetic acid 400 parts of distilled water at 60 are poured over the paste with constant agitation and the whole boiled for a short time. The solution is diluted with 7600 parts of distilled water, and 2 parts of glacial acetic acid are added. 100 parts of Orlon (registered trademark) are entered in this bath at 60. The material was pretreated for 10-15 minutes at 60 in a bath of 8000 parts of water and 2 parts of glacial acetic acid. The dyebath is brought to 100 in 30 minutes, boiled for 1 hour and the material rinsed. A level yellow dyeing of excellent light fastness and very good wet fastness is obtained.

' Pad dyeing Example B A padding liquor is prepared with:

50 grams per liter of dye (corresponding to the dyeing preparation produced in the previous dyeing example) 3 grams per liter of sodium alginate 5 grams per liter of acetic acid conc.

20 grams per liter of a cationic softener e.g. a condensation product of 1 mol stearic acid and 1 mol triethanolamine i Polyacrylonitrile fiber material is padded cold by the usual method on a 2 or 3 bowl pad. The pick-up is 80%.

' After intermediate drying for a short time at 90 on tenters, in a hot flue or by infrared radiation, the material is fixed for 1-3 minutes with dry air at 170-190 on tenters, subsequently rinsed, soaped and rinsed again. A yellow dyeing with excellent light fastness is obtained. T extz'le printing example A printing paste is made up with:

Parts Dye (corresponding to the dyeing preparation produced in the previous dyeing example) 75 Acetic acid cone; 10 Sodium alginate thickening 450 A cationic softener, e.g. a condensation product of 1 mol stearic acid and 1 mol triethanolamine 25 Glaubers salt 25 Water 415 1000 Polyacrylonitrile fiber material is printed according to the usual hand-block printing process and subsequently air-dried, steamed for 20-30 minutes in a star steamer with saturated steam, rinsed, soaped, rinsed again and dried. On polyacrylonitrile fabrics a yellow print with very good fastness properties is obtained.

In the following tables 1, 2, 3 and 4 the symbols K to K represent the following groupings: I

| 1 X K1 the grouping -N(C2Hr)2 NH:

I K, the grouping -HaCI;T-C2H5] X9 G9 I K0 the grouping H5C-1}I@] Xe e K5 the grouping HzN-N H x ea K0 the grouping nzN-l v H 1 X NHCrHr 9 K11 the grouping --N (02115) 2 The symbols K to K and the anion X in the individually presented dyes are chosen from the series displayed above or in the specification respectively. These groupings or anions can be exchanged in any of these dyes for another grouping or another anion in the series; Thus, the symbols K to K may appear in place of K It may therefore be noted as fundamental that in these dyes the symbol K with a given number may in each instance be exchanged for any other symbol K having a member different from it.

Further valuable basic dyestufis, which can be produced by the procedures given in the above Examples .1 to 10 are described in the following table.

They correspond to the formula ll io R9 l ia R11 GB Rn- N=N Ru i iou x l l Rn Ria 1km R s wherein the symbols R -R have the meanings assigned them in the said table.

The anion X may be any one .of those named in the specification.

Example Rn R10 R11 R12 R1: 14

CH; 11 H H H l 1'COCH:-K

CH; 12 H SOgNHz H l lczHuKa CH 13 01 NO: H ILCOCHz-Kz CH 14 N H NO: ON CH3 COOH2--K1 02115 15 N H NO; H H

\C0-CH2'K3 CnHa 16 CO-N 11 N0, 01 CH;

C;H K

CH 17 OON NO: H H

C2H4K10 18 SO3N H No, H H

CzH4-K1 19 SO7N H NO: H Cl CzH4--Kg 20 NHSO2CflH4 K1 H N02 H NO:

CH 21 N H No: H CI CzH5 22 N H NO; H 01 S02C2H4Ku 23 H H SOzN-CzHA-Kn H H CH 24 SOg1 ICzH4-K1 H NO: H H

CH 25 H COAICzH4-K9 H OH Example R15 Rm R11 R1: Shage of the Dyeipg on e olyacrylomtnle Anion X C2H4OH 11 H N OCzH5 H Orange O1 CzH4CN 12 H N(C2H5)z H H (10 Cl 13 H N(C:H5)z H H Bordeaux C1 14 H N(CzH5)2 H H Violet CH SO CgH4CN 15 H N H H Scarlet OH S0 CgH 16 H N(C:H4OH)2 H H BTOWH Cl 17 H N(C2H5)2 H H Orange C1 C2H4CN 18 Cl N H H Red Cl Example R Rm R11 Rm Shade of the Dy 011 Polyacrylonitrile Anion X 19 H N(CH )1 H H Red H50; H N(CH3)1 H H Ruby CH SO4 21 H N(C:Hs)z H H Bordeaux Cl N(C2H5)z H H (10 C1 H H OH Yellow CH3SO4 OH4ON2 24 H N H H Red- C1 \OQHI; H H OH; H Yellow '01 Further valuable basic dyes which can be produced by the procedures given in the above Examples 1 to 10 are described in the following table.

wherein the symbols Rm-Rgo have the meanings assigned 20 them in said table.

The anion X may be any one of those named in the They correspond to the formula specification.

R20 R10 R R20 R R N N 28 Anion X 30 Rn R25 R24 21 Ex. R19 R20 R21 R22 R23 R24 R25 CaHs 26 C ON H No: H H H CgHb 27 s- SOnN H 7 NO: H H H CzH4-Ka CH3 28 SOgI ICqH4-Kn H 7 NO: H H H CH; 29 SOzI I-C2H4K1o H NO: H H H 3 0211s 30 SO2N-C2H4K1 H NO: H H H 01 H NO: H H H B1 H N01 NO: H H

CH3 v 33 SO I I-OaH4Ko H NO: H H H on; 34 H H SO2'-I 1'C1H4K1 H H H CH3 7 35 SOfllI-CzHr-Kl H NO: H H H 36 H H SOzNCaH4-Kz H H H 7 CH3 37 H H SO21 ICnH4Ka H H H CH 38 H H SQa1 TC2H4-K4 H H H I CH3 39 H H SOzIkCzHr-Ku H H H 1 16 can be produced by the pro cedures given in the above wherein the symbols R -R have the meanings assigned Examples 1 to 10 are described in the following table. them in said table.

They correspond to the formula The anion X may be any one of those named in the v specification.

es R01 85- I I R N=NCOR74 0,

l ivu R11 Rmfg\ 1H1 Anign X-e Example R01 R R09 R70 R11 45 CH H CH CHZNHOOCfil-Kl OH; 46 OH; H CH CII NHOOGHg-Kn CH3 47 OH; H CH3 CH NHCOOH -Kg CH; H OH; CHQNHCOCHQK1 CH3 H CH3 GHzNHOOCHz-Km OH:

H CH3 CH2NUCOOHQK1 011 H CH; OHRNHCOCHfl-Kq CH3 H CH3 CHgNHCOCHr-Ka OH; H CH3 CHgNHCOCHn-Ka CH3 H OH; CH NHCOGHz-K1 OH; H 0H,NHoooH,Km 0H3 H H OHQNHC 0 CHz-K7 CH3 H H CHzNHOOOHz-K; 0H3 H H CHzNHOOOHz-Ks 0H3 H H CH3 OHzNHCOGHn-Ks H H cmNHooom-m OCH; H No, CH CHzNHCOCHQ-Kl OOH;

H H H H H NHOOOH: H H

H NHCOOCzHu H H H COOCzHu H H R73 R14 Shade of the dyeing on Anion X Polyacrylonitrile H CH Yellow 01 H ooNH, do 01 CH3 CH3 do c1 CgH4CN CH3 --do OHaSdt oflH-ioH CH3 ..--do OHaSQl CH3 do -Q. CHQSOA l 51 0H 0 CH; Mao Hsol 52. 0H Q-NO; CH3 7 Reddish-yellow 01 5a 0H -C -NH-o0om 0H3 Yellow o1 Example Rn R7: R14 shagglggiglyifigli on Anion 54 OH -4111, CH3 yellow c1 55 0H SOs-0H CH3 Greenish-yellow. 01

5s OH SOr-N(CH3)2 CH3 do 01 57 OH sol-Outt CH3 do 01 58 NH; CH3 -d0 01 59 OH 0 0000133 Yellow omsol 1 60 OH OH; Reddlsh-yellow H804 s1 NH, OHz-CHOHQ CH3 Orange Hsol 62 OH 0-011 CH; Yellow oHasol dm-rrnooom-m e3 OH CE-[3 V CH3 I -do o1 CHg-NHC 0 CHz-Ki E e4 OH Q-om OH; --do o1 ()HaNHO 0 0111-11,

65 OH @0113 cm do o1 CH NHC o CHrKm Further valuable basic dyes which can be produced by wherein the symbols R75-R30 have the meanings assigned the procedures given in the above Examples 1 to 10 are them in said table.

described in the following table. The anion X may be any one of those named in the 65 They correspond to the formula specificatlon.

R71- N=N-Rao Anion X in R10 7 l 75 m U mmz 6 -Em Mo ie M 36 o omzamo 56 o o omz m 6 8 o momzoomoooo m -M 560 omz mo m oooomz M 6 i w EQ AEUEZO omnwo 0 0 m M mo o omzamo m 560 o 0M2 m m mo olw 6 omfibfigm n; 05 6 M MO o omz mo "mo 0 -3 How 6 4 m nTO mZoowwo o 05 6 M moo omzsmo "mo 0 -ow s6 :6 6 6 m a ms 6 omwo o 05 6 M7500 omz mo mo o 5 50% XEQZ STK 6 EM 25 26 o M amo o omzfio m6 0 -wh 6 m 52 a6 0 M mo o omzamo a6 0 -R 6 8 EO O Ow Mw OZ Q moo omz mo mo woo 2 5mm 5% 0 0 o mw oz M WO o omzfio E0 mo o -E. l ombwnowfiow @N 6.54 'Dom no m u 3 2M EN 2 2m 2% 0355mm 5; E0 0 M NO o omz mo E0 02 m ..::::..3 mo

Jvm 6 8m m m 62 m 5 2 Q fio o o wz mo 6 zo m o o o o mo oz moo M smooomzsmu "mo oz M 8 6 3 umo E00 M mo o omz mo E0 oz m 5 XU W2 6 8 Ho moo M mo o owz mo "in 02 m 8 6 8 mo e o mo o o o m "moo Q mooomZfio mo oz m \0 0 mo 6 3 0 0 m mooomzamo wmoooomz m m mw 5mm 8 Eo om mo o w o m m M awoo omzsmo 55o oomz m w 5 *ow mo 5; 0 0 o mw o o 05 m Q mo o omz mo E6 0 o omz m m mw zo m w EJV Z wow mo Em EY EQ l m M moo omzfio 55 oo omz m m ww om aoriom M 55 23 no 5 m m M 5m 5H m fi m 3. A basic dye according to claim 1, said basic dye being of the formula 4. A basic dye according to claim 1, said basic being of the formula I N H2 NEE-CH3 9 5. A basic dye according to claim 1, said basic dye being of the formula 6. A basic dye according to claim 1, said basic dye being of the formula NH; CH3 GB H oH4-1 I-02s N=N c HaC-C \NH References Cited UNITED STATES PATENTS 2,357,317 9/ 1944 Dickey 260205 2,955,108 10/1960 Omietanski 260-205 3,183,224 5/1965 Benz et a1. 260-446 3,190,871 6/1965 Auerbach et a1 260146 3,206,451 9/1965 Benz et al 260--153 CHARLES B. PARKER, Primary Examiner. F. D. HIGEL, Assistant Examiner. 

1. A BASIC DYESTUFF OF THE FORMULA 